Multifunctional resins for 3d printed materials and methods of making same

Abstract

Described herein are polymers prepared from multifunctional monomers, according to a defined sequential reaction scheme in a one-pot system, along with methods of making the same. Also described herein are tunable, 3D printed materials prepared from resin mixtures described herein. The 3D printed materials possess a large range of material properties, including tunable elastic moduli properties.

What is claimed is: 
     
         1 . A method of polymerizing functionalized monomers, comprising:
 subjecting an initial precursor resin mixture to an external stimulus, wherein the initial precursor resin mixture comprises one or more monomers, the one or more monomers comprising multifunctional monomers comprising two or more functional groups, to generate an intermediate stage reactive conversion having a spatially defined initial polymer length; and   subjecting the intermediate stage reactive conversion to one or more polymerization and/or crosslinking stimuli,   wherein the method steps are performed in a single reactor.   
     
     
         2 . The method of  claim 1 , wherein the two or more functional groups are each independently selected from the group consisting of an alkene, a thiol, an azide, a diene, or an oxime. 
     
     
         3 . The method of  claim 1 , wherein the multifunctional monomer comprises a bifunctional monomer, a trifunctional monomer, or a tetrafunctional monomer. 
     
     
         4 . The method of  claim 1 , wherein the initial precursor resin mixture further comprises a single-functionality monomer having one functional group. 
     
     
         5 . The method of  claim 4 , wherein the one functional group is selected from the group consisting of an alkene, a thiol, an azide, a diene, or an oxime. 
     
     
         6 . The method of  claim 1 , wherein the external stimulus is a light source. 
     
     
         7 . The method of  claim 1 , wherein the external stimulus is a raised temperature. 
     
     
         8 . The method of  claim 7 , wherein the raised temperature is from about 50° C. and about 175° C. 
     
     
         9 . The method of  claim 1 , wherein the external stimulus is ultrasound. 
     
     
         10 . The method of  claim 1 , wherein the one or more polymerization and/or crosslinking stimuli is a light source. 
     
     
         11 . The method of  claim 1 , wherein the one or more polymerization and/or crosslinking stimuli is a raised temperature. 
     
     
         12 . The method of  claim 11 , wherein the raised temperature is from about 50° C. and about 175° C. 
     
     
         13 . The method of  claim 11 , wherein the polymerization and/or crosslinking stimuli comprise to at least two different raised temperatures. 
     
     
         14 . The method of  claim 1 , wherein the initial precursor resin mixture further comprises a photoinitiator. 
     
     
         15 . The method of  claim 1 , wherein the intermediate stage reactive conversion is partially crosslinked or polymerized. 
     
     
         16 . The method of  claim 1 , wherein the method is a 3D printing method. 
     
     
         17 . A polymeric material made by a method of  claim 1 . 
     
     
         18 . The polymeric material of  claim 17 , having a modulus gradient in a spatial direction. 
     
     
         19 . The polymeric material of  claim 18 , wherein the modulus gradient is an elastic modulus gradient. 
     
     
         20 . The polymeric material of  claim 18 , wherein the modulus ranges from 10 2  Pa to 10 10  Pa.